JP2013542297A - Method for producing polycarbonate polyol by immortal polymerization of cyclic carbonate - Google Patents

Abstract

  The present invention relates to a method for producing a polycarbonate polyol, wherein the cyclic carbonate is polymerized in the presence of a chain transfer agent comprising a DMC catalyst and a polyether carbonate polyol.

Description

  The present invention relates to a method for producing a polycarbonate polyol by immortal polymerization of a cyclic carbonate in the presence of a chain transfer agent comprising a double metal cyanide catalyst (DMC catalyst) and a polyether carbonate polyol.

  Immortal polymerization within the scope of the present invention means ring-opening polymerization, wherein the cyclic carbonate reacts with ring-opening in the presence of a chain transfer molecule. In the ideal case, when there is no chain termination reaction when the polymerization occurs and the number of resulting macromolecules is equal to the number of chain transfer molecules used, the polymerization is referred to as immortal. In immortal polymerization, the molecular weight of the resulting polymer can be adjusted by the ratio of the number of monomer molecules used to the number of chain transfer molecules. The functionality of the resulting polymer is determined by the functionality of the chain transfer molecule.

  Polymer (1992), No. 33 (9), pages 1941 to 1948 describes living polymerization of neopentyl glycol carbonate using a tetraphenylporphyrin aluminum complex as a catalyst. Since the reaction was carried out without using a chain transfer agent, the molecular weight of the resulting polymer is determined by the number of catalyst molecules. The disadvantage is that the functionality of the generated polymer is not controlled. Another disadvantage is the poor sensitivity of the catalyst to trace amounts of water and the industrial availability of the catalyst.

  Journal of Polymer Science, Part A (2000), No. 38 (16), pp. 2861-2871 uses epoxides, lactones and methacrylate esters using metalloporphyrin aluminum and metalloporphyrin zinc. Immoral polymerization of episulfides has been described. Protonic compounds such as carboxylic acid and HCl are used as the chain transfer agent. The use of alcohols as chain transfer agents is limited to epoxides and lactones, and the catalysts used are reactive towards large amounts of alcohol groups, so low molecular weight alcohols are not suitable as starters. Another disadvantage is the poor sensitivity of the catalyst to trace amounts of water and the industrial availability of the catalyst. Details of the experiment are not mentioned in the publication.

  Macromolecules (2001), No. 34 (18), pp. 6196-6201 describe immortal polymerization of lactones and lactides using aluminum complexes as catalysts. The disadvantage is the use of benzyl alcohol as the monofunctional chain transfer molecule. Another disadvantage is the poor sensitivity of the catalyst to trace amounts of water and the industrial availability of the catalyst.

  Chemistry-A European Journal (2008), No. 14 (29), pages 8772-8775 describes immortal polymerization of trimethylene carbonate using benzyl alcohol as a chain transfer agent. The disadvantage is the use of monofunctional chain transfer molecules. Macromol. Rapid Commun. (2009), No. 30 and No. 2128 to 2135 describe the use of dihydroxy compounds as starters. The disadvantage of both studies is the use of a zinc imidate complex as a catalyst, which is not readily industrially available and is reactive to air, so the reaction requires strict deactivation. It is.

  EP-A 1859863 and DE-A 10108485 describe the conditioning of DMC (double metal cyanide) catalysts for the polymerization of epoxides. The catalyst in this reaction is disadvantageous in that it is sensitive to a large amount of alcohol groups in the starter, and therefore low molecular weight alcohol is not suitable as a starter.

  WO-A 03/014186 discloses DMC-catalyzed ring-opening homopolymerization and copolymerization of cyclic carbonates, optionally in the presence of one or more starter compounds (chain transfer agents). As transfer agents, polyether polyols and polyester polyols are described, among others. However, polyether carbonate as a chain transfer agent is not disclosed.

European Patent Application No. 1859863 German Patent Application No. 10108485 International Publication No. 03/014186

Polymer (1992), No. 33 (9), pp. 1941-1948 Journal of Polymer Science, Part A (2000), 38 (16), pp. 2861-2871 Macromolecules (2001), 34 (18), 6196-6201 Chemistry-A European Journal (2008), No. 14 (29), No. 8772-8775 Macromol. Rapid Commun. (2009), No. 30, pp. 2128-2135

  It is an object of the present invention to provide a method for the immortal polymerization of cyclic carbonates, wherein the resulting polycarbonate polyol has a molecular weight distribution that is not substantially broad compared to the molecular weight distribution of the chain transfer agent. Differentiated. In a preferred embodiment, the resulting polycarbonate polyol should have a primary OH group content of at least 80%.

  Surprisingly, a cyclic carbonate is polymerized in an immortal polymerization using a DMC catalyst, and a polyether carbonate polyol is used as a chain transfer agent, resulting in a molecular weight distribution that is not substantially wide compared to the molecular weight distribution of the chain transfer agent. It has now been found that polycarbonate polyols can be produced.

  Accordingly, the present invention provides a method for producing a polycarbonate polyol, characterized by polymerizing a cyclic carbonate in the presence of a chain transfer agent comprising a DMC catalyst and a polyether carbonate polyol. Polyether carbonate polyols or mixtures of different polyether carbonate polyols can be used as chain transfer agents. Cyclic carbonates or mixtures of different cyclic carbonates can be used as cyclic carbonates.

  The present invention further provides a polycarbonate polyol produced by the process according to the present invention. The polycarbonate polyols produced by the process according to the invention contain polyether groups and can therefore be regarded as polyether carbonate polyols. In order to distinguish it from the chain transfer agent used, the product obtained by the process according to the invention is called polycarbonate polyol.

  The weight ratio of the chain transfer agent used to the cyclic carbonate used is preferably 1: 0.001 to 1:50, particularly preferably 1: 0.005 to 1: 5, very particularly preferably 1: 0.005 to 1: 1. .

The process according to the invention is preferably carried out in the presence of 10 to 2000 ppm of DMC catalyst. The preferred reaction temperature is 60 to 160 ° C, particularly preferably 80 to 130 ° C. An excessively high reaction temperature is disadvantageous because an ether group is formed by the cleavage of CO ₂ .

  The reaction time is generally 1 to 48 hours, preferably 2 to 24 hours, as a result of which cyclic carbonates are generally no longer present in the reaction mixture. Alternatively, the completion of reaction conversion is monitored and continued until cyclic carbonate is no longer present in the reaction mixture. For example, the progress of the reaction can be monitored by suitable analytical methods (eg IR after sample removal, NMR spectroscopy, chromatographic methods) or can be determined purely experimentally by comparative tests.

  The process according to the invention may be carried out in the presence or absence of an inert solvent such as toluene, chlorobenzene, 1,2-dichloroethane, 1,2-dimethoxyethane or dioxane. Preferably, the process according to the invention is carried out in the absence of an inert solvent.

〔式中、
R₁、R₄およびR₅は、互いに独立して水素または直鎖状または分岐鎖状のC1〜C12アルキル基またはC6〜C10アリール基を表し、ならびに
R₂およびR₃は、互いに独立して水素または直鎖状または分岐鎖状のC1〜C12アルキル基またはC6〜C10アリール基またはアリルオキシメチル基を表す〕
の化合物である。 The cyclic carbonates according to the invention have the formulas (I) and (II):

[Where,
R ₁ , R ₄ and R ₅ independently of one another represent hydrogen or a linear or branched C1-C12 alkyl group or C6-C10 aryl group, and
R ₂ and R ₃ independently of each other represent hydrogen, a linear or branched C1-C12 alkyl group, a C6-C10 aryl group, or an allyloxymethyl group.
It is a compound of this.

  Preferred compounds of formula (I) are trimethylene carbonate, neopentyl glycol carbonate, 2,2,4-trimethyl-1,3-pentanediol carbonate, 2,2-dimethyl-1,3-butanediol carbonate, 1, 3-butanediol carbonate, 2-methyl-1,3-propanediol carbonate, 2,4-pentanediol carbonate, 2-methyl-butane-1,3-diol carbonate, TMP-monoallyl ether carbonate and pentaerythritol diallyl ether Carbonate. Trimethylene carbonate and neopentyl glycol carbonate are particularly preferred.

  Preferred compounds of formula (II) are ethylene carbonate, propylene carbonate and phenylethylene carbonate.

Very particular preference is given to compounds of the formula (I). In the immortal polymerization of cyclic carbonates according to formula (I), these compounds do not produce ether groups in the presence of a chain transfer agent consisting of a DMC catalyst and a polyether carbonate polyol, or very little by cleavage of CO _2. Only has the advantage of producing.

  In a highly preferred embodiment of the invention, a compound of formula (I) where R1 = R4 = H or a compound of formula (II) where R5 = H is used. Examples of formula (I) are trimethylene carbonate, neopentyl glycol carbonate and 2-methyl-1,3-propanediol carbonate. An example of formula (II) is ethylene carbonate. This is advantageous in that polycarbonates containing primary OH groups as end groups can be obtained by using these cyclic carbonates.

  DMC catalysts are known and are described in US-A 3404109, US-A 3829505, US-A 3941849 and US-A 5158922. Improved DMC catalysts are described in US-A 5470813, EP-A 700949, EP-A 743093, EP-A 761798, WO-A 97/40086, WO-A 98/16310 and WO-A 00/47649. ing. It is preferred to use a DMC catalyst according to EP-A 700949, which, in addition to the double metal cyanide compound (eg zinc hexacyanocobalt (III)) and an organic complex ligand (eg tert-butanol), Also included are polyether polyols having number average molecular weights greater than moles. For the tests described in the examples, a DMC catalyst comprising polypropylene glycol having a number average molecular weight of 1000 g / mol is used.

Polyether carbonate polyol is used as a chain transfer agent. Polyether carbonate polyols within the scope of the present invention also contain ether groups in addition to carbonate groups, and are prepared, for example, by catalytic addition of alkylene oxide (epoxide) and carbon dioxide to an H-functional starter material (starter). This reaction is shown schematically in Scheme (III), where R represents an organic group such as alkyl, alkylaryl or aryl, each of which may also contain heteroatoms such as O, S, Si, etc. and n And m represents an integer, and the product shown in Scheme (III) for a polyether carbonate polyol may repeat in principle in the polyether carbonate polyol from which a block having the indicated structure was obtained. Is merely understood as being able to vary the sequence, number and length of the blocks and the OH functionality of the starter and is not limited to the polyether carbonate polyols shown in Scheme (III). Cyclic carbonates (eg R = CH ₃ propylene carbonate) shown in scheme (III) form as further products.

  Preferably, polyether carbonate polyols are used as chain transfer agents, which are carbon dioxide and alkylene oxides (eg propylene oxide) to H-functional starter materials (starters) catalyzed by double metal cyanides (DMC catalysts). , Epichlorohydrin, styrene oxide, cyclohexene oxide, butene oxide, etc.). Corresponding production methods are described, for example, in EP application 10000511.5, WO-A 2008/013731 or US-A 20030149232.

  Hydroxy functional polycarbonates can also be used as chain transfer agents. Hydroxy functional polycarbonates can be made, for example, by condensation of a diol with cleavage of an alkyl alcohol and an open chain dialkyl carbonate. Another manufacturing method for hydroxy-functional polycarbonates is alkylene oxides (eg ethylene oxide, propylene oxide) to H-functional starter materials (eg glycerol, propylene glycol and its higher homologues, ethylene glycol and its higher homologues, etc.). And / or butylene oxide, etc.) and carbon dioxide catalyzed addition, alkylene oxide and carbon dioxide are incorporated alternately. In general, a homogeneous zinc or cobalt catalyst is used for this purpose.

A particularly preferred embodiment of the present invention is a process for producing a polycarbonate polyol, comprising:
(I) placing an H-functional starter material, or a mixture of at least two H-functional starter materials, into a reaction vessel, removing water and / or other readily volatile compounds as needed ("drying"); Provided that a DMC catalyst, an H-functional starter material, or a mixture of at least two H-functional starter materials is added before or after drying,
(Ii) adding alkylene oxide and carbon dioxide to the mixture formed from step (i) ("copolymerization" to form a polyether carbonate polyol chain transfer agent);
(Iii) The mixture formed from step (ii) (including DMC catalyst, polyether carbonate polyol and cyclic carbonate) is added to cyclic carbonate and optionally (further) DMC catalyst (DMC used in step (i)) Which may be the same as or different from the catalyst), wherein the cyclic carbonate may be the same or different from the cyclic carbonate contained in the mixture formed from step (ii), from step (ii) The weight ratio of the resulting mixture to the added cyclic carbonate is 1: 0.001 to 1:50, particularly preferably 1: 0.005 to 1: 5, very particularly preferably 1: 0.005 to 1: 1. It is a method characterized by reacting at a temperature of 60 to 160 ° C., particularly preferably 80 to 130 ° C.

Step (i):
To produce a polyether carbonate polyol by catalytic addition of alkylene oxide (epoxide) and carbon dioxide to an H-functional starter material (starter) in the presence of a DMC catalyst according to the present invention, an H-functional starter material, or at least 2 A mixture of two H-functional starter materials is placed in a reaction vessel and water and / or other readily volatile compounds are removed as needed. This is done, for example, by stripping with nitrogen or carbon dioxide (under reduced pressure if necessary) or by vacuum distillation at a temperature of 50 to 200 ° C., preferably 80 to 160 ° C., particularly preferably 100 to 140 ° C. This pre-treatment of the starter material, or mixture of starter materials, is simply referred to hereinafter as drying.

  The DMC catalyst may already be present in the H-functional starter material or a mixture of at least two H-functional starter materials. However, after drying, the dried DMC catalyst can also be added to the H-functional starter material or a mixture of H-functional starter materials. The DMC catalyst can be added to the H-functional starter material in solid or suspension form. If the catalyst is added as a suspension, it is preferably added before drying the H-functional starter material.

Preferably, an activation step is performed after step (i), particularly preferably where a partial amount (based on the total amount of alkylene oxide used in the copolymerization) of one or more alkylene oxides is produced from step (i). This addition of a partial amount of alkylene oxide can be carried out in the presence or absence of CO ₂ , temperature peaks that occur as a result of subsequent exothermic chemical reactions (“hot spots”), and / or Or observe the waiting period as needed until a pressure drop in the reactor occurs. When performing the activation process in the absence of CO ₂ , the hot spot becomes more apparent.

Step (ii):
The metered addition of one or more alkylene oxides and carbon dioxide can be carried out simultaneously or sequentially and can be added in such a way that the total amount of carbon dioxide is metered in at one time or over the reaction time. Preferably, carbon dioxide is metered in. The metered addition of one or more alkylene oxides is carried out simultaneously or continuously with the metered addition of carbon dioxide. If a large amount of alkylene oxide is used in the synthesis of the polyether carbonate polyol, the metering can then be carried out simultaneously or sequentially by separate metering or one or more metering, wherein at least two alkylene oxides are added. Metered as a mixture. Depending on the mode of metered addition of alkylene oxide and carbon dioxide, it is possible to synthesize random, alternating, block or gradient polyether carbonate polyols.

Since excess carbon dioxide is advantageous because it reacts slowly, excess carbon dioxide is preferably used based on the calculated amount of carbon dioxide incorporated in the polyether carbonate polyol. The amount of carbon dioxide can be set by the total pressure under the reaction conditions. A total pressure (absolute pressure) in the range of 0.01 to 120 bar, preferably 0.1 to 110 bar, particularly preferably 1 to 100 bar has been found to be advantageous for the copolymerization for the production of polyether carbonate polyols. ing. The process according to the invention is that the copolymerization for the production of polyether carbonate polyols is carried out at 50 to 150 ° C., preferably 60 to 145 ° C., particularly preferably 70 to 140 ° C. and very particularly preferably 90 to 110 ° C. Is further shown to be advantageous. Setting the temperature below 50 ° C stops the reaction. At temperatures above 150 ° C., the amount of undesirable by-products is greatly increased. Furthermore, it should be ensured that CO ₂ changes from the gaseous state to the liquid and / or supercritical state as much as possible under the selected reaction conditions. However, CO ₂ can also be added to the reactor in the form of a solid, in which case CO ₂ can be changed to a liquid and / or supercritical state under selected reaction conditions.

Preferred reactors for producing polyether carbonate polyols are tube reactors, stirred tanks and loop reactors. The addition of alkylene oxide and CO ₂ can be carried out independently of one another, batchwise, semi-continuously (semi-batch) or continuous. For safety reasons, if propylene oxide or ethylene oxide is used, the content of free alkylene oxide in the reaction mixture in the stirred tank should not exceed 15% by weight (eg WO-A 2004/081082; page 3 See line 14). Thus, in both the semi-batch operation where the product is not removed until the end of the reaction and the continuous operation where the product is continuously removed, particular attention should be paid to the metered rate of epoxide addition. The metered rate of epoxide addition should be adjusted so that the epoxide reacts sufficiently fast and completely despite the carbon dioxide suppression effect. Carbon dioxide can be supplied continuously or discontinuously. This depends on whether the epoxide is consumed fast enough and if the product optionally contains CO ₂ -free polyether blocks. The amount of carbon dioxide (shown as pressure) can be varied during the addition of the epoxide as well. It is possible to maintain the pressure of CO ₂ during the addition of the epoxide stepwise increased, or low comb or the same.

  A further possible embodiment in the stirred tank is a continuous addition of starter (CAOS treatment). However, it is not necessary to add the starter continuously or partially. It may already be present in the total amount at the start of the reaction.

In general, alkylene oxides having 2 to 24 carbon atoms can be used for the process according to the invention. Alkylene oxides having 2 to 24 carbon atoms are, for example, ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide. 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2 -Methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene Oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide, butadiene monooxide, isoprene monooxide, cyclopentene oxide, cyclohexene oxide, cyclohepte Or poly - - oxide, cyclooctene oxide, styrene oxide, methyl styrene oxide, mono-pinene oxide, mono-, as diglycerides and triglycerides epoxidized fats, epoxidized fatty acids, C ₁ -C ₂₄ esters of epoxidized fatty acids, Epikurorohido Phosphorus, glycidol, and derivatives of glycidol such as methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and the like and epoxide functional alkyloxy silanes such as 3-glycidyloxypropyltrimethoxysilane, 3 -Glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropyl Chill dimethoxysilane, 3-glycidyloxy propyl ethyl diethoxy silane, one or more compounds selected from the group comprising 3-glycidyloxy propyl triisopropoxy silane. As the alkylene oxide, ethylene oxide and / or propylene oxide, particularly propylene oxide is preferably used.

As a suitable H-functional starter material (also referred to as “starter”), a compound having a hydrogen atom active against alkoxylation can be used. Groups having an active hydrogen atom and active against alkoxylation are, for example, —OH, —NH ₂ (primary amine), —NH— (secondary amine), —SH and —CO ₂ H. -OH and -NH ₂ are preferred, and -OH is particularly preferred. Examples of H-functional starter substances include water, monohydric or polyhydric alcohols, monohydric or polyhydric amines, polyhydric thiols, carboxylic acids, amino alcohols, aminocarboxylic acids, thioalcohols, hydroxy esters, polyether polyols, polyester polyols. Polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polyethylene imines, polyether amines (eg, so-called Jeffamine® from Huntsman, eg D-230, D-400, D-2000, T-403, T -3000, T-5000 or a corresponding product manufactured by BASF, such as polyetheramine D230, D400, D200, T403, T5000, etc., polytetrahydrofuran (for example PolyTHF (registered trademark) manufactured by BASF, for example PolyTHF (registered trademark) 250, 650S, 1000, 1000S, 1400, 1800, 2000), polytetrahydrofuran amino (BASF product polytetrahydrofuranamine 1700), polyether thiol, polyacrylate polyol, castor oil, monoglyceride or diglyceride of ricinoleic acid, monoglyceride of fatty acid, chemically modified monoglyceride of fatty acid, diglyceride and / or triglyceride, and average at least per molecule One or more compounds selected from the group comprising C ₁ -C ₂₄ alkyl fatty acid esters containing two OH groups are used. _C 1 _{-C 24} alkyl fatty acid esters that contain per molecule on average at least two OH groups, for example, Lupranol Balance (TM) (BASF SE), Merginol (TM) type (Hobum Oleochemicals GmbH), Sovermol (R ) Type (Cognis Deutschland GmbH & Co. KG) and Soyol (registered trademark) TM type (USSC Co.).

  Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds. The following can be used as monofunctional alcohols: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyne- 1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1 -Pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine. The following are suitable as monofunctional amines: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine. The following can be used as monofunctional thiols: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, Thiophenol. Monofunctional carboxylic acids include the following: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.

  Polyhydric alcohols suitable as H-functional starter materials are, for example, dihydric alcohols (eg ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butene. Diol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, methylpentanediol (eg, 3-methyl-1,5-pentanediol), 1,6-hexanediol; 1,8-octane Diol, 1,10-decanediol, 1,12-dodecanediol, bis- (hydroxymethyl) -cyclohexane (eg 1,4-bis- (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycol, Dipropylene glycol, tripropylene glycol, polypropylene Recall, dibutylene glycol and polybutylene glycol); trihydric alcohols (eg trimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil etc.); tetrahydric alcohols (eg pentaerythritol etc.); polyalcohols (eg sorbitol, Hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, especially castor oil, etc.), and modified products of the above alcohols with various amounts of ε-caprolactone.

The H-functional starter material can also be selected from the material types of polyether polyols, in particular polyether polyols having a molecular weight M _n in the range of 100 to 4000 g / mol. Preferably, it is a polyether polyol composed of repeating units of ethylene oxide and propylene oxide, preferably has a content of propylene oxide units of 35 to 100%, particularly preferably contains 50 to 100% of propylene oxide units Have quantity. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide. Suitable polyether polyols composed of propylene oxide and / or ethylene oxide repeating units are, for example, Desmophen®, Acclaim®, Arcol®, Baycoll®, from Bayer MaterialScience AG, Bayfill (R), Bayflex (R), Baygal (R), PET (R) and polyether polyols (e.g. Desmophen (R) 3600Z, Desmophen (R) 1900U, Acclaim (R) Polyol 2200 , Acclaim (R) Polyol 4000I, Arcol (R) Polyol 1004, Arcol (R) Polyol 1010, Arcol (R) Polyol 1030, Arcol (R) Polyol 1070, Baycoll (R) Poly BD 1110, Bayfill (Registered trademark) VPPU 0789, Baygal (registered trademark) K55, PET (registered trademark) 1004, polyether (registered trademark) S180, and the like. Further suitable homopolyethylene oxides are for example Pluriol® E brand from BASF SE, suitable homopolypropylene oxides are for example Pluriol® P brand from BASF SE, suitable ethylene oxide and propylene. Mixed copolymers of oxide are, for example, Pluronic® PE or Pluriol® RPE brand from BASF SE.

The H-functional starter material can also be selected from polyester polyols, in particular polyester polyols having a molecular weight M _n in the range of 200-4500 g / mol. As the polyester polyol, at least a bifunctional polyester is used. The polyester polyol preferably consists of alternating acid and alcohol units. Examples of the acid component include succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the above-mentioned acids and / or Or a mixture of anhydrides is used. Examples of alcohol components include ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4 Use -bis- (hydroxymethyl) -cyclohexane, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or a mixture of the above alcohols. When a divalent or polyvalent polyether polyol is used as an alcohol component, a polyester ether polyol that can be similarly used as a starter material for producing a polyether carbonate polyol is obtained. Preferably, polyether polyols having M _n = 150 to 2000 g / mol are used for the production of polyester ether polyols.

Furthermore, polycarbonate diols, in particular polycarbonate diols having a molecular weight M _n in the range from 150 to 4500 g / mol, preferably from 500 to 2500 g / mol, can be used as H-functional starter substances, for example phosgene, dimethyl carbonate, diethyl It is prepared by reaction of carbonate or diphenyl carbonate and a bifunctional alcohol or polyester polyol or polyether polyol. Examples of polycarbonates are found, for example, in EP-A 1359177. For example, as the polycarbonate diol, Desmophen (registered trademark) C type manufactured by Bayer MaterialScience AG, such as Desmophen (registered trademark) C 1100 or Desmophen (registered trademark) C 2200, can be used.

  In a further embodiment of the invention, a polyether carbonate polyol can be used as the H-functional starter material.

  H-functional starter materials generally have a functionality of 1 to 8, preferably 2 or 3, i.e. the number of H atoms active in the polymerization per molecule. The H-functional starter material is used either alone or in the form of a mixture of at least two H-functional starter materials.

Preferred H-functional starter materials are those of the general formula (IV):
HO— (CH ₂ ) _x —OH (IV)
[Wherein x is a number from 1 to 20, preferably an even number from 2 to 20]
Of alcohol. Examples of alcohols according to formula (IV) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol. Further preferred H-functional starter materials are neopentyl glycol, trimethylol propane, glycerol, pentaerythritol, reaction products of alcohols and ε-caprolactone according to formula (IV), for example the reaction product of trimethylol propane and ε-caprolactone Products, reaction products of glycerol and ε-caprolactone, and reaction products of pentaerythritol and ε-caprolactone. More preferred polyether polyols composed of water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyalkylene oxide repeating units as the H-functional starter material.

The H-functional starter material is particularly preferably ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1 , 3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, bifunctional and trifunctional polyether polyols Wherein the polyether polyol is composed of a di- or tri-H functional starter material and propylene oxide, or a di- or tri-H functional starter material, propylene oxide and Consists of ethylene oxide. The polyether polyol preferably has a molecular weight _{Mn in} the range of 62-4500 g / mol and a functionality of 2-3, in particular a molecular weight _{Mn in} the range of 62-3000 g / mol and a functionality of 2-3. .

Step (iii):
In order to increase the concentration of the DMC catalyst in the reaction mixture, a DMC catalyst can be added in step (iii).

  However, surprisingly, it was found that the polyether carbonate polyol chain transfer agent produced from step (ii) still contains a DMC catalyst having sufficient catalytic activity for the subsequent immortal polymerization, so in step (iii) It is preferred not to add a DMC catalyst. Therefore, the advantage of this embodiment is that the DMC catalyst required for the immortal polymerization of cyclic carbonate is already present in the chain transfer agent.

Step (iii) is preferably carried out in the presence of 10 to 2000 ppm of DMC catalyst. The preferred reaction temperature is 60 to 160 ° C, particularly preferably 80 to 130 ° C. If the reaction temperature is too high, then ether groups are generated by cleavage of CO ₂ , which is disadvantageous.

  The reaction time in step (iii) is generally from 1 to 48 hours, preferably from 2 to 24 hours, so that generally cyclic carbonates are no longer present in the reaction mixture. Also monitor the completion of the conversion of the reaction according to step (iii) and continue until the cyclic carbonate is no longer present in the reaction mixture. The progress of the reaction can be monitored, for example, by suitable analytical methods (eg IR after sample removal, NMR spectroscopy, chromatographic methods) or can be determined purely experimentally by comparative tests.

  The process according to step (iii) can be carried out in the presence or absence of an inert solvent such as toluene, chlorobenzene, 1,2-dichloroethane, 1,2-dimethoxyethane or dioxane. The process according to the invention is preferably carried out in the absence of an inert solvent.

  In another embodiment of the present invention, a polycarbonate polyol produced by the method of the present invention is used as a chain transfer agent. This is therefore a process for producing a polycarbonate polyol, characterized in that a cyclic carbonate is polymerized in the presence of a DMC catalyst and a polycarbonate polyol (as a chain transfer agent) produced by the process according to the invention. To that end, the polycarbonates and cyclic carbonates used as chain transfer agents are preferably in a weight ratio of 1: 0.001 to 1:50, particularly preferably 1: 0.005 to 1: 5, very particularly preferably 1: 0.005 to 1: 1. Use. These polycarbonate polyols used as chain transfer agents are pre-manufactured in a separate reaction step.

  The process according to the invention makes it possible to obtain polycarbonate polyols which have a molecular weight distribution which is not broad or substantially broad compared to chain transfer agents and which are distinguished by a distinct OH functionality. By appropriately selecting the cyclic carbonate, the ratio between the primary and secondary OH groups in the end groups can be adjusted. When trimethylene carbonate, neopentyl glycol carbonate, 2-methyl-1,3-propanediol carbonate or ethylene carbonate is used as the cyclic carbonate, a polycarbonate polyol containing only primary OH groups as terminal groups is obtained.

  Compared with the secondary OH group, the primary OH group has a high reactivity, for example, a high reactivity in a reaction with an isocyanate that forms a urethane portion. In the reaction of polyols with diisocyanates and / or polyisocyanates, this results in faster curing of the material. The fields of use are the production of flexible foams, rigid foams, thermoplastic urethanes (TPU), adhesives and also in surface coating compositions and dispersions. The target sector is, among other things, manufacturers of prepolymers and polyurethane materials.

  The process according to the invention can be carried out without complicated inert gas techniques and can proceed fast at moderate temperatures, preferably with inert solvents such as toluene, chlorobenzene, 1,2-dichloroethane, 1,2-dimethoxyethane or Does not require dioxane or the like. A high content of primary OH end groups can also be achieved only by using ethylene oxide in the production of polyether carbonate. However, the use of ethylene oxide is problematic for workplace safety and toxicity reasons. Under the reaction conditions of polyether carbonate production, the DMC catalyst side reaction between ethylene oxide and carbon dioxide to give cyclic ethylene carbonate is significant in the presence of carbon dioxide.

  The weight average molecular weight and number average molecular weight of the produced polymer were determined by gel permeation chromatography (GPC). Procedure according to DIN 55672-1: “Gel permeation chromatography, part 1—tetrahydrofuran as eluent”. A polystyrene sample of known molar mass was used for calibration.

  Polydispersity is the ratio of weight average molecular weight to number average molecular weight. The polydispersity is used within the scope of the present invention to evaluate the width of the molecular weight distribution, that is, the higher the polydispersity value, the wider the molecular weight distribution.

The OH number was determined based on DIN 53240-2, but N-methylpyrrolidine was used instead of THF / dichloromethane as the solvent. Titration was performed using 0.5 mol of ethanol KOH (end point recognition by potentiometric method). Castor oil having the specified OH number was used as a test substance. The display unit in “mg _KOH / g” is mg [KOH] / g [polyether carbonate polyol].

The ratio of produced propylene carbonate to polyether carbonate polyol was determined by NMR spectroscopy (Bruker, 400 Ultrashield, 400 MHz, 16 scans). Samples were dissolved in deuterated chloroform in each case. The relevant resonances in ¹ H-NMR (based on TMS = 0 ppm) are as follows:
-Polyether polyol (ether part in a polymer in which no carbon dioxide is incorporated): Region A, resonance at 1.11 to 1.17 ppm, including resonance regions corresponding to 3 H atoms,
Carbonates derived from carbon dioxide incorporated in polyether carbonate polyols: region B, resonance at 1.25 to 1.32 ppm, including resonance regions corresponding to 3 H atoms,
Cyclic carbonate: region C, resonance at 1.45 to 1.49 ppm, including resonance region corresponding to 3 H atoms,
Unreacted propylene oxide: region D, resonance at 2.95-2.99 ppm, including resonance region corresponding to one H atom,
Unreacted trimethylene carbonate: 4.46 and 2.15 ppm, including resonance regions corresponding to regions E and F, 4 and 2 H atoms,
Trimethylene carbonate incorporated into the polymer: regions G and H, 4.24 and 2.05 ppm, including resonance regions corresponding to 4 and 2 H atoms.

に従ってモル％へ変換した。 The amount of carbonate incorporated into the polymer in the reaction mixture is calculated as follows:
In view of the relative strength, the amount of polymer bound carbonate (“linear carbonate” LC) in the reaction mixture is determined by the formula (V):

Converted to mol%.

に従って計算した。 The weight content (% by weight) of polymer-bound carbonate (LC ′) in the reaction mixture is expressed by the formula (VI):

Calculated according to

The coefficient 102 is obtained from the sum of the molar mass of CO ₂ (molar mass 44 g / mol) and the molar mass of propylene oxide (molar mass 58 g / mol), and the coefficient 58 is obtained from the molar mass of propylene oxide.

に従って計算した。 The amount (mol%) of unreacted propylene oxide (PO) in the reaction mixture is expressed by the formula (VII):

Calculated according to

に従って計算した。 The amount (mol%) of cyclic carbonate (CC ′) in the reaction mixture is expressed by the formula (VIII):

Calculated according to

に従って計算した。 The amount (mol%) of unreacted trimethylene carbonate (TMC) in the reaction mixture is represented by the formula (IX):

Calculated according to

¹⁹ F-NMR spectroscopy to determine the ratio of primary OH groups to secondary OH groups was performed according to ASTM International Standard Test Method D4273-05 (Appendix). The signal for the primary OH group was observed in the range of -75.23 to -75.33 ppm, and the signal for the secondary OH group was observed at -75.48 to -75.57 ppm.

Example 1
(A) Production of polyether carbonate diol (chain transfer agent) by copolymerization of propylene oxide (PO) and CO ₂ in the presence of polypropylene glycol as a starter
A mixture of 7.9 mg DMC catalyst (prepared according to Example 6 of WO-A 01/80994) and 13.3 g polypropylene glycol (starter, molecular weight 1000 g / mol) was placed in a 300 ml pressure reactor and slightly depressurized ( 50 mbar), and a little argon was flowed, and the mixture was stirred at 130 ° C. for 1 hour (500 rpm). After applying 15 bar of CO ₂ pressure, 9.5 g of propylene oxide (PO) was metered in using an HPLC pump (1.0 ml / min). The reaction mixture was stirred at 130 ° C. for 15 minutes (stirring speed 500 / min). An additional 33.0 g of PO was then metered in using an HPLC pump (1.0 ml / min). When the addition was complete, stirring was continued for an additional 3 hours at 130 ° C. Samples taken after the reaction time were analyzed by NMR spectroscopy. This mixture contained polyether carbonate containing 10.5 mol% carbonate units, 0.1 mol% propylene oxide and 1.1 mol% cyclic propylene carbonate corresponding to 17.1 wt% carbon dioxide.

Low molecular weight components were removed from the mixture on a rotary evaporator and samples were analyzed by NMR spectroscopy. 39.4 g of a mixture of polyether carbonates containing 10.8 mol% carbonate units, 0.0 mol% propylene oxide and 1.1 mol% cyclic propylene carbonate were obtained. ^The ratio of primary OH groups to secondary OH groups was determined to be 11.6 / 88.4 by ¹⁹ F NMR spectroscopy. The resulting polyether carbonate had a molecular weight M _n = 6520 g / mol, M _w = 9530 g / mol and a polydispersity of 2.06. The OH number of the obtained mixture was 25.7 mg _KOH / g.

(B) Reaction of the polyether carbonate diol obtained from step a) with trimethylene carbonate (immortal ring-opening polymerization using a DMC catalyst)
10.5 g of DMC catalyst (prepared according to WO-A 01/80994, example 6), 20.1 g of the polymer from example 1 (a) and 20.1 g of trimethylene carbonate are placed in a 300 ml pressure reactor. The pressure was reduced (p = 75 mbar), and the mixture was stirred for 30 minutes at 110.degree. Then 1.5 bar of argon pressure was applied and stirring was carried out at 110 ° C. for 3 hours.

The yield of the polymer mixture was quantitative. NMR spectroscopy of the reaction mixture showed complete conversion of trimethylene carbonate. ^The ratio of primary OH groups to secondary OH groups was determined to be 82.8 / 17.2 by ¹⁹ F NMR spectroscopy. The resulting polyether carbonate had a molecular weight _Mn = 12,780 g / mol, _Mw = 18,720 g / mol and a polydispersity of 1.46. The OH number of the obtained mixture was 16.8 mg _KOH / g.

Example 2
(A) Production of polyether carbonate triol (chain transfer agent) by copolymerization of propylene oxide (PO) and CO ₂ in the presence of polypropylene triol as a starter
Add 300 ml of a mixture of 8.1 mg DMC catalyst (prepared according to Example 6 of WO-A 01/80994) and 8.5 g Arcol Polyol 1110 (starter, molecular weight 700 g / mol, functionality 3, OH number 235 mg _KOH / g) Placed in a pressure reactor, slightly depressurized (50 mbar), flushed with a little argon and stirred at 130 ° C. for 1 hour (500 rpm). After applying 15 bar of CO ₂ pressure, 9.5 g of propylene oxide (PO) was metered in using an HPLC pump (1.0 ml / min). The reaction mixture was stirred at 130 ° C. for 15 minutes (stirring speed 500 / min). An additional 33.0 g of PO was then metered in using an HPLC pump (1.0 ml / min). When the addition was complete, stirring was continued for an additional 3 hours at 130 ° C. Samples taken after the reaction time were analyzed by NMR spectroscopy. A mixture of polyether carbonates containing 8.8 mol% carbonate units corresponding to 14.5 wt% carbon dioxide, no unreacted propylene oxide, and 1.3 mol% cyclic propylene carbonate was obtained.

Low molecular weight components were removed from the mixture on a rotary evaporator and samples were analyzed by NMR spectroscopy. 38.9 g of a mixture of polyether carbonates containing 10.9 mol% carbonate units, no unreacted propylene oxide and 1.5 mol% cyclic propylene carbonate was obtained. ^The ratio of primary OH groups to secondary OH groups was determined to be 11.7 / 88.3 by ¹⁹ F NMR spectroscopy. The resulting polyether carbonate had a molecular weight M _n = 5620 g / mol, M _w = 7340 g / mol and a polydispersity of 1.31. The resulting mixture had an OH value of 40.0 mg _KOH / g.

(B) Reaction of the polyether carbonate triol obtained from step a) with trimethylene carbonate (immortal ring-opening polymerization using DMC catalyst)
10.3 g DMC catalyst (prepared according to Example 6 of WO-A 01/80994), 20.2 g of the polymer from Example 1 (a) and 20.1 g of trimethylene carbonate are placed in a 300 ml pressure reactor. The pressure was reduced (p = 75 mbar), and the mixture was stirred for 30 minutes at 110.degree. Then 1.5 bar of argon pressure was applied and stirring was carried out at 110 ° C. for 3 hours.

The yield of the polymer mixture was quantitative. NMR spectroscopic analysis of the reaction mixture resulted in 78.2% conversion of trimethylene carbonate. ^The ratio of primary OH groups to secondary OH groups was determined to be 79.8 / 20.2 by ¹⁹ F NMR spectroscopy. The resulting polyether carbonate had a molecular weight M _n = 11,600 g / mol, M _w = 18,630 g / mol and a polydispersity of 1.61. The OH number of the obtained mixture was 21.6 mg _KOH / g.

Claims (11)

  A method for producing a polycarbonate polyol, wherein a cyclic carbonate is polymerized in the presence of a chain transfer agent comprising a DMC catalyst and a polyether carbonate polyol. Cyclic carbonates are represented by formulas (I) and (II):

[Where,
R1, R4 and R5 each independently represent hydrogen or a linear or branched C1-C12 alkyl group or C6-C10 aryl group, and R2 and R3 each independently represent hydrogen or linear or Represents a branched C1-C12 alkyl group or a C6-C10 aryl group or an allyloxymethyl group]
2. The method of claim 1, wherein the method is selected from at least one compound of the group comprising:   Cyclic carbonates are trimethylene carbonate, neopentyl glycol carbonate, 2,2,4-trimethyl-1,3-pentanediol carbonate, 2,2-dimethyl-1,3-butanediol carbonate, 1,3-butanediol Carbonate, 2-methyl-1,3-propanediol carbonate, 2,4-pentanediol carbonate, 2-methyl-butane-1,3-diol carbonate, TMP-monoallyl ether carbonate, pentaerythritol diallyl ether carbonate, propylene carbonate The method of claim 1, wherein the method is selected from at least one compound in the group comprising phenylethylene carbonate and ethylene carbonate.   The process according to claim 1, wherein zinc hexacyanocobalt (III) comprising tert-butanol as the organic complex ligand and a polyether polyol having a number average molecular weight greater than 500 g / mol is used as the DMC catalyst.   The process according to claim 1, characterized in that trimethylene carbonate is used as the cyclic carbonate.   The process according to claim 1, characterized in that the polymerization of the cyclic carbonate is carried out at a reaction temperature of 60 to 160 ° C in the presence of a DMC catalyst and at least one chain transfer agent.   The process according to claim 1, characterized in that the weight ratio of chain transfer agent to cyclic carbonate is from 1: 0.001 to 1:50. (I) placing an H-functional starter material, or a mixture of at least two H-functional starter materials, into a reaction vessel, removing water and / or other readily volatile compounds as needed ("drying"); However, the DMC catalyst, H-functional starter material, or a mixture of at least two H-functional starter materials is added before or after drying,
(Ii) adding alkylene oxide and carbon dioxide to the mixture formed from step (i) ("copolymerization" to form a polyether carbonate polyol chain transfer agent);
(Iii) adding a cyclic carbonate to the mixture produced from step (ii), wherein the cyclic carbonate may be the same or different from the cyclic carbonate contained in the mixture produced from step (ii); The weight ratio of the mixture formed from (ii) to the cyclic carbonate to be added is 1: 0.001 to 1:50, and the product mixture is reacted at a temperature of 60 to 160 ° C. The method according to 1.   The process according to claim 8, characterized in that no DMC catalyst is added in step (iii).   The method according to claim 1, characterized in that the polycarbonate produced by the method according to claim 1 is used as a chain transfer agent.   An aliphatic polycarbonate obtainable by the method according to claim 1.